4-(2&#39;- or 4&#39;-pyridylethylamino)-azobenzene dyes



United States Patent US. Cl. 260-156 12 Claims ABSTRACT OF THE DISCLOSURE Disperse dyes of the 4-(2- or 4-pyridyl-ethyl-amino)- azobenzene series yield extremely fast dyeings on fibers and fiber materials made of fully synthetic or semi-synthetic high molecular organic materials of hydrophobic character. Fastness properties include fastness to heatsetting, sublimation, pleating, gas fumes, ozone, crossdyeing, dry-cleaning, lubricants, chlorine and wet treatments.

This application is a continuation-in-part of application Ser. No. 481,384, filed Aug. 20, 1965, and now abandoned.

The present invention provides new, substantially waterinsoluble dyestuffs of the formula l CH2 GHQ-Z BN=N N wherein B is phenyl substituted with from one to three substituents selected from the group consisting of chloro, bromo, lower alkoxy, cyano, nitro, lower alkylsulfonyl and di (lower alkyl) aminosulfonyl; or a nitronaphthyl radical;

R is hyrogen, lower alkyl, lower hydroxyalkyl, lower cyanoalkyl, lower alkanoyloxyalkyl, lower choroalkanoyloxyalkyl, lower hydroxyalkanoyloxyalkyl, lower cyanoalkanoyloxyalkyl, lower alkoxycarbonyloxyalkyl, lower acetylalkyl, lower acetylalkanoyloxyalkyl, lower cyanoalkoxyalkyl, lower phenylarninocarbonyloxyalkyl or methoxycarbonylethyl;

R is hydrogen, lower alkyl, lower alkoxy, formylamino,

lower alkanoylamino, lower hydroxyalkanoylamino, lower alkoxycarbonylamino or lower alkylsulfonylamino;

R is hydrogen, lower alkyl or lower alkoxy;

R is hydrogen or lower alkoxy and Z is Z-pyridyl or 4-pyridyl.

The term lower says that the respective alkyl group contains l to 4, preferably 1 or 2 carbon atoms.

For the manufacture of the new dyestuffs of this invention an aminoazo dyestuff of the formula BN=N N l l R1 R2 R3 (II) is reacted with a 2- or 4-vinyl-pyridine of the formula CH =CH-Z (III) or the diazonium compound from an amine of the formula BNH

is reacted with a coupling component of the formula lower chloroalkanoylamino, r

ice

R2 R3 (V) The known aminoazo dyestuffs of Formula II are reacted with a vinylpyridine of Formula III in analogy with the processes described in J. Am. Chem. Soc. 77, 4913, 5434, (1955), J. Am. Chem. Soc. 78, 4127, (1956) or J. prakt. Chemie (4), 4, 19, (1956).

The reaction with a vinylpyridine of the Formula III can be performed in a particularly advantageous manner in the liquid phase, frequently with advantage in the presence of a saturated fatty acid containing 1 to about 5 carbon atoms, for example formic, acetic, propionic, butyric or isobutyric acid; of an alkyl ester, such as ethyl acetate of ethyl propionate; of an anhydride, for example acetic or propionic anhydride; of a heavy-metal salt, such as copper, zinc, cobalt or nickel formate or acetate; of a monohydric or polyhydric alcohol, for example ethyleneglycol or glycerol; or of a phenol, such, for example, as phenol, meta-cresol, para-cresol or a cresol mixture; or of water.

When both reactants used are liquid, the reaction may be performed without a solvent, in the presence of about 0.1% to 10% of one of the aforementioned additives, or a solvent or diluent may be additionally used. Suitable solvents are large amounts of the aforementioned additives, provided they are liquid, or other inert liquids, for example aromatic hydrocarbons which may contain halogen atoms or nitro or alkoxy groups. When solid reactants are used, it is especially useful to add such a solvent. The reaction temperature is most advantageously chosen within the rangefrom about 20 to 150 C., preferably from 50 to 130 C. When acetic acid is used, the reaction is most advantageously performed at 50 to C. Under the conditions described the reaction takes a few hours.

According to the second variant of the present process, a coupling component on which the aminoazo dyestuffs of the Formula II are based, that is to say an amine of the formula is reacted in the manner described above with a compound of the Formula III and the reaction product of the Formula V is coupled in the usual manner with a diazonium compound from an amine of the Formula IV, for example in an acid medium (which may 'be buffered) (while cooling, for example at 0 to 5 C.

The dyestuffs obtained are valuable new disperse dyestuffs. It is especially advantageous to convert them in known manner into dyestuff preparations prior to their use. For this purpose they are disintegrated until their average particle size is about 0.01 to 10 especially about 0.1 to 5a. This disintegration may be carried out in the presence of a dispersant of filler. For example, the dried dyestuff is grounded together with a dispersant, if desired or required in the presence of a filler, or kneaded with a dispersant to form a paste and then dried under vacuum or spray-dried. When a suitable proportion of water is added to a preparation manufactured in this manner, it may be used for dyeing or padding from a dilute liquor or for printing.

For dyeing from dilute liquors there are generally used up to about 50 g. of dyestulf per litre, for padding up to about g. per litre, preferably up to 100 g. per litre, and for printing up to about 150 g. per kilogram of printing paste. The goods-to-liquor ratio may vary within Q wide limits, for example from 1:3 to 1:200, preferably from 1:3 to 1:80.

From an aqueous suspension the new dyestuffs are absorbed very well by mouldings from fully synthetic or semisynthetic organic substances of high molecular weight. They lend themselves especially well for dyeing, padding or printing fibres, filament or fleeces, 'woven or knitted fabrics from polyesters, cellulose'2 /2-acetate or cellulose triacetate. They are also suitable for dyeing synthetic polyamides, polyolefins, acrylonitrile polymers and polyvinyl compounds. Particularly valuable dyeings are obtained on linear aromatic polyesters. These esters are in general polycondensates from terephthalic acid and glycols, especially ethyleneglycol. On these materials they are easy to apply. They show rapid dyeing, good migration (levelling), and are capable of producing deep colours, i.e. their build up properties are very good.

Dyeing follows the usual practice: Polyester fibres can be dyed in the presence of carriers at temperatures from about 80 C. to 125 C. or in the absence of carriers under superatmospheric pressure at about 100 to 140 C. by the exhaustion method. Furthermore, polyester fibres may be padded, impregnated or printed with aqueous dispersions of the new dyestuffs, the dyestuffs being heat-set on the impregnated material at about 140 to 230 C., for example with the aid of steam or air. In the particularly favourable temperature range from 180 to 220 C. the dyestuffs diffuse rapidly into the polyester fibre without subsequent sublimation, even when the material under treatment is exposed to such a temperature for a prolonged period. In the manner the objectionable fouling of the dyeing apparatus is prevented. Cellulose-2V2- acetate is preferably dyed bewteen about 65 and 80 C. and cellulose triacetate at a temperature of up to about 115 C. The most advantageous pH range is from 2 to 9, especially from 4 to 8. The absorption rate of cellulose- 2 /2-acetate, cellulose triacetate and polyesters for the new dyestuffs is excellent and is hardly affected by a preliminary heat-setting or stretching of the polyester fibres.

As a rule, the usual dispersants, which are preferably anionic or nonionic and may also be used in the form of mixtures of two or more, are added. About 0.5 g. of dispersant per litre of dyestuff preparation will generally suffice though larger amounts, for example up to about 3 g. per litre, may be used equally well. Known anionic dispersants suitable for use in the present process are, for example, condensates from naphthalenesulphonic acids and formaldehyde, especially dinaphthylmethanedisulphonates, esters of sulphonated succinic acid, Turkey red oil and alkali metal salts of sulphuric acid esters of fatty alcohols, for example sodium laurylsulphate, sodium cetylsulphate, sulphite cellulose waste liquor or alkai meta salts thereof, soaps or alkali metal sulphates of monoglycerides of fatty acids. Examples of known and particularly suitable nonionic dispersants are the adducts of about 3 to 40 mols of ethylene oxide with alkylphenols, fatty alcohols or fatty amines and neutral sulphuric acid esters thereof.

In padding and printing the conventional thickener's may be used, for example modified or unmodified natural products, for example alginates, British gum, gum arabic, crystal gum, locust bean flour, tragacanth, carboxymethyl cellulose, hydroxyethyl cellulose, starches or synthetic products, for example polyacrylamides r polyvinyl alcohols.

The dyeings obtained are extremely fast, for example outstandingly fast to heat-setting, sublimation, pleating gas fumes, ozone, crossdyeing, dry-cleaning, lubricants, chlorine, and wet treatments, being, for example, fast to water, sea water, washing and perspiration.

Reserve effects on wool and cotton are good, as is the suitability for discharge printing. The fastness to light is very good, even in dainty shades so that the new dyestuffs may also be used with advantage as mixing components for the production of fashionable pastel shades. Some of the dyestuffs obtained by the present invention are fast to boiling and reduction at temperatures of up to at least 220 C., and especially a 80 to 140 C.; this stability is not impaired within the pH range from 4 to 10 by the goods-to-liquor ratio used or by the presence of dyeing accelerators. By virtue of their stability these new dyestuffs are particularly suitable for dyeing polyester/ cotton blend fabrics by the single-bath method in combination with substantive reactive dyestuffs.

In the molecular structure of the disperse dyes according to this invention each azo nitrogen atom is directly bound to a ring carbon atom of an aromatic, e.g. phenyl or naphthyl, nucleus. Parts and percentages in the following examples are by weight.

EXAMPLE 1 A mixture of 23.4 parts of 4-vinylpyridine, 24.2 parts of N-ethylaminobenzene and 12 parts of acetic acid of 100% strength is stirred for 6 hours at 110 C., whereupon the acetic acid, the excess 4-vinylpyridine and any residual N-ethyl-aminobenzene are distilled off under a pressure of 15 mm. Hg at 70 C. The N-ethyl-N-[2'-(4"- pyridyl) ethyl] aminobenzene obtained in this manner is sufiiciently pure for the manufacture of the dyestutf.

In the meantime a diazo solution is prepared in the following manner: 17.2 parts of 1 amino 2 chloro- 4-nitro-benzene in a mixture of 60 parts of Water and 40 parts of concentrated hydrochloric acid are stirred for 3 hours at room temperature. The resulting suspention is cooled by adding 100 parts of ice and diazotized at 0 to 5 C. within 2 hours With a solution of 6.9 parts of sodium nitrite in 100 parts of water. The batch is stirred on for 15 minutes, whereupon the resulting solution is mixed with 10 parts of aminosulphonic acid and filtered. A solution of 22.6 parts of N-ethyl-N-[2'-(4- pyridyl) -et'hyl] -aminobenzene in 50 parts of glacial acetic acid is added to the clear diazoniurn salt solution and the coupling reaction is finalized in the acid medium by adding sodium acetate until a pH value of 4 has been reached. The dyestuff is suctioned off, washed free from acid and dried. After having been recrystallized from ethanol, it melts at 117 C.; it corresponds to the formula l CzEs Instructions for use 7 parts of the dyestuif obtained inExample 1, 4 parts of sodium dinaphthylmethandisulphonate, 4 parts of sodium cetylsulphate and 5 parts of anhydrous sodium sulphate are ground to a fine powder for 48 hours in a ball mill. 2 parts of the dyeing preparation thus obtained are dispersed in 3000 parts of water containing 3 parts of a 30% solution of a highly sulphonated castor oil and parts of an emulsion of a chlorinated benzene in water. 100 parts of polyester fibre fabric (Dacron, registered trademark) are immersed at 20 to C. in the dyebath which is then heated within about minutes to to C. and dyeing is carried on for 1 hour at 95 to 100 C. The fabric is then taken out of the bath, washed, soaped for 15 minutes at 70 C. with a solution of 0.1% strength of an alkylphenyl polyglycol ether, once more Washed and dried. The resulting ruby red dyeing possesses good properties of fastness.

When dyeing is performed in a high-temperature dyez do mo 2 50 do Ia Ill: Ill r. Z cmo umo 1 L AU AU 1 1 1 H I Z z z 2o zo m 0 Z w f m E Xm 530:3 9 2m wQEEmxo m m mz wm. N m mz vmm wfiowfiow on: yo wwfimgw u nomoafi mo o sn om Q 111-11%11. m m m G HHOOOOE O HHHHHM m. w 96% m 5m m m m oEooooES E 6 S m 33 E60 w moo mz E6 H mu m 4 M ..%11. i m HOO EZ EG W HHHHH mamwmfi mfi PPH E .5 18...: m m iolooolmzl m HHHHHHHHHPH 1 2 5 ..%11. m G qto oo mz m 5Q o oo3w ma 08mm .HHNO 011 HM 110G111: Hm .1 0U 1 1 nm 0Q TmUihQ v HH m 1 1 obofid md wdHmw HM from? mm ofldmm 1 1 1 1 I 1 mm ..%...1 m m umoLowlmzl .1....HHmnnafififimfifiwww mfim:MHHH n m m mc mo oo mz HHHPHWU Q m m fio wo mb oo mz 8 Q ..%...1 m m @oooo E/ 1 5 1%.:1 m m wo ooo mz w 2 w 6 62 3 m 1%..... m E mo o w mz m 1 2 i fi32 3 EE 2.. m m m m O HZO o 055 a2 55 1-32.5. m m m 76550561 HHHHHHHHHHHHHHHH HHnnnnun 6 m ..%...1 i m m mooofiooooi o B :5 500 i 50 36$ 1%.11 m m Eo ma :8 mm 6 3 m ..%1:. m m E 500055 HHHJHHHHHPH 5 m m m E m 56000055 mm oQ 11111 imwwfm v HH HH HM .1. 0w PwoQw mm w nm 1 mm gm ..%.1.. m m Eo 1 H E QEY EM F E U2 Q5-H 111111111 ow I. 1 HM Hm EHHU 1111111111111111111111 o oQ m mm mamm 111111111111111111111111111111111111111111111111111 cc 11111111 1 on n m m m HHOQOOES 3 m 68H 111.11%.11 m m m Eoooooflmo E fi fi Y i Q Q m i m H m o 0 0 o o m o 2 m m m omo fiz 56 0 0 o O EO O 3 a2 1.1-1.510 11... n .l H 0w 111 111111111111111111111111111111111111111111111111111 0w 111111111111111 mm d g 11111 1. low}... mOO m $00M. o ofla ma wamm I... w oQm mm uamw 3 5 1%..... 500 m Eo E6 3:2 35 d 1.1%. 1 E m m "mo 00 E wfi QQPEFYOQQQ fi 1 En :%.11 m E mo oo mg m 3 3 55 6Q on m m E m o EQEQoEE Eo -m Q m E 5 0 55 A Jifii fiv HQ 3 13am ...........%1:. E m E6 i i fifiu N Hwm 6Q 6.5 mm 3.5m m m H H.101. 3J2E6o5fim 1 .5 52.5 E EQ m m w 6 1 EEQ EQQ b m 6m 83933 N m "G m 5 m 02 QM co uugm EXAMPLE 43 o2rrl-0-ooom Having thus disclosed the invention what we claim: 1. Substantially water-insoluble dyestuff of the formula wherein cyanoalkoxy(lower)alkyl, lower phenylaminocarbonyloxyalkyl or methoxycarbonylethyl;

R is hydrogen, lower alkyl, lower alkoxy, formylamino, lower alkanoylamino, lower chloroalkanoylamino, 1ower hydroxyalkanoylamino, lower alkoxycarbonylamino or lower alkylsulfonylamino;

R is hydrogen, lower alkyl or lower alkoxy;

R is hydrogen or lower alkoxy and Z is Z-pyridyl or 4-pyridyl.

2. Dyestufr' according to claim 1 of the formula 3. Dyestutf according to claim 1 of the formula 4. Dyestuff according to claim 1 of the formula 5. Dyestuff according to claim 1 of the formula CH2-CH2- 6. Dyestuif according to claim 1 of the formula 7. Dyestuff according to claim 1 of the formula C Hr-CN Cilia-CH2 N 8. Dyestulf according to claim 1 of the formula C l I /C 0 Hz- C II2- 9. Dyestuff according to claim 1 of the formula I CH:

10. Dyestuif according to claim 1 of the formula I CHs 1 12 11. Dyestuff according to claim 1 of the formula References Cited N02 UNITED STATES PATENTS l 2,234,723 3/1941 Dickey et a1. 260156 021w N=N- N 2,830,043 4/1958 Merian 260207.1 011z 011, 5 3,268,507 8/1966 Kruckenberg 260207 SO2-CHz CH3 FLOYD D. HIG'EL, Primary Examiner 12. Dyestuif according to claim 1 of the formula US. Cl. X.R.

CN v

84, 41, so, 71; 117--138.8, 143, 144; 26037, 41, 205, om N=NON 207.1, 290, 294.1, 295, 296 

